Boranediyl‐ and Diborane(4)‐1,2‐diyl‐Bridged Platinum A‐Frame Complexes

• Published in: Chemistry : a European journal Vol. 26; no. 39; pp. 8518 - 8523
• Main Authors: Brunecker, Carina, Müssig, Jonas H., Arrowsmith, Merle, Fantuzzi, Felipe, Stoy, Andreas, Böhnke, Julian, Hofmann, Alexander, Bertermann, Rüdiger, Engels, Bernd, Braunschweig, Holger
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 14.07.2020; John Wiley and Sons Inc
• Subjects: Bonding; Boranes; Boron; Boron compounds; Chemistry; Communication; Communications; Diborane; EDA-NOCV; oxidative addition; Platinum; platinum; EDA-NOCV; boron; bonding; oxidative addition
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202001168

Diplatinum A‐frame complexes with a bridging (di)boron unit in the apex position were synthesized in a single step by the double oxidative addition of dihalo(di)borane precursors at a bis(diphosphine)‐bridged Pt02 complex. While structurally analogous to well‐known μ‐borylene complexes, in which delocalized dative three‐center‐two‐electron M‐B‐M bonding prevails, theoretical investigations into the nature of Pt−B bonding in these A‐frame complexes show them to be rare dimetalla(di)boranes displaying two electron‐sharing Pt−B σ‐bonds. This is experimentally reflected in the low kinetic stability of these compounds, which are prone to loss of the (di)boron bridgehead unit. (Di)boron‐bridged platinum A‐frame complexes were synthesized by the twofold oxidative addition of dihalo(di)boranes to a bis(diphosphine)‐bridged diplatinum(0) precursor. Experimental and theoretical studies show that these compounds are rare (di)boranediyl complexes with electron‐sharing Pt−B bonds.